KR20010111590A - Composition comprising mercapto-functional compounds - Google Patents

Abstract

The present invention provides a compound comprising at least two or more olefinically unsaturated groups comprising at least one electron-drawing functional group connected to a carbon atom of an unsaturated bond; A composition comprising a compound comprising at least two mercapto-functional groups and a catalyst comprising optionally at least one NH-group blocked. The invention also relates to the application of the composition and the use of the composition as a coating composition or adhesive.

Description

A composition comprising a mercapto-functional compound {COMPOSITION COMPRISING MERCAPTO-FUNCTIONAL COMPOUNDS}

The present invention relates to a composition comprising:

Compounds comprising at least two olefinically unsaturated groups comprising at least one electron-drawing functional group connected to a carbon atom of an unsaturated bond;

Compounds comprising at least two mercapto-functional groups; And

- catalyst.

Unsaturated groups such as acryloyl groups can react with active hydrogen-containing compounds. The reaction is believed to involve the addition of anions derived from nucleophilic, active hydrogen-containing compounds that act as donors to the active unsaturated groups that serve as receptors. When the active hydrogen-containing compound is a C-H compound such as malon ester or acetoacetate, the reaction is known as Michael addition reaction. SH-compounds are also known to act like active hydrogen-containing compounds in a reaction mechanism similar to the Michael addition reaction. In the following, the reaction mechanism of the SH-compound is referred to as thio-Michael reaction.

Compositions as described in the starting paragraphs cured by the thio-michael reaction are known from European patent application EP-A 0 160 824. Catalysts mentioned in the above specification are quaternary ammonium compounds, tetramethyl guanidine, diaza-bicyclo-undecene and diaza-bicyclo-nonene. Thio-Michael reaction catalyzed by the strong base is difficult to control. The reaction takes place too quickly or not at all depending on the concentration of catalyst used. Tertiary amines are present but do not react at room temperature according to the above disclosure. In addition, base-catalyzed reactions undergo acid inhibition. Carbon dioxide or acidic substances present in the air partially inhibit or even retard cross reactions.

US 2,759,913 describes a process for the copolymerization of mercapto-functional compounds of unsaturated monomers and basic catalysts such as trimethyl benzyl ammonium hydroxide. As mentioned above, the reaction with the catalyst is difficult to control.

British patent application GB-A 2,166,749 describes compounds comprising a curable coating composition comprising an unsaturated polyester at room temperature and a catalyst which is at least three thiol groups and tertiary amines such as triethyl amine. However, as shown in the examples in GB-A 2,166,749, the reaction takes about 16 hours to cure at room temperature. Faster reactions will only occur at higher temperatures.

It is an object of the present invention to provide a composition which overcomes the above-mentioned drawbacks.

It is an object of the present invention to achieve a composition of the type mentioned in the opening paragraph which comprises a catalyst comprising at least one NH-group optionally blocked.

Surprisingly, although the art has taught that a strong basic catalyst is needed, the thio-michael curable compositions comprising the catalyst according to the invention show rapid cure at room temperature. This is evidence of the advantage that short production times are possible. Energy costs can be saved because curing takes place at room temperature. In addition, comparing the Michael and thio-Michael reactions catalyzed by strong bases, the reaction time depends much less on the amount of catalyst. This is advantageous for ease of formulation. It is also known that the treatment can be carried out with low viscosity oligomers. This has the advantage that a composition can be prepared which contains little if the solvent still cannot spray. The reactors involved in the curing reaction are much less toxic than other reactive or coating compositions, such as those which can be most cross-reactive in isocyanates. After curing, the applied layer resists hydrolysis and degradation. In addition, the thermal stability of sulfide bonds is high.

In compounds comprising at least two olefinically unsaturated groups, the olefinically unsaturated group comprises at least one electron-drawing functional group connected to the carbon atom of the unsaturated bond. Olefinically unsaturated bonds are double or triple bonds. Preferably, the olefinically unsaturated group of the compound comprising at least two olefinically unsaturated groups has a structure according to formula (I):

(In Formula 1, at least one of R 1, R 2, R 3 and R 4 includes an electron-drawing functional group connected to a carbon atom of an unsaturated bond and at least one of R 1, R 2, R 3 and R 4 includes at least divalent valences. Connected to the valence)

Examples of electron-drawing functional groups are carbonyl, carboxyl, ester, thiocarbonyl, thiocarboxyl, thioester, sulfoxide, sulfonyl, sulfo, phosphate, phosphite, phosphonite, phosphinite, nitro, nitrile And amides.

In the case of monovalent R1, R2, R3 and / or R4, the hydrogen-atom, chain or branched alkyl, cycloalkyl, in which the electron-drawing functional group is optionally substituted with various other functional groups, such as carboxylic acids or hydroxides, Attached to alkenyl, cyclo-alkenyl, alkynyl, cyclo-alkynyl and aryl. If it does not include an electron-drawing functional group, R 1, R 2, R 3 and / or R 4 are independently hydrogen atoms, chain or branched alkyl, cycloalkyl, optionally substituted with various functional groups, such as carboxylic acids or hydroxides, Alkenyl, cyclo-alkenyl, alkynyl, cyclo-alkynyl and aryl. When at least one R 1, R 2, R 3 and R 4 is linked to a multiatomic group and not an electron-drawing functional group, it is a simple bond. The polyvalent functional group is connected to at least two functional groups according to formula (1). Polyvalent functional groups are selected from simple bonds, substituted or unsubstituted alkylenes, cycloalkylenes, alkenylenes, cycloalkenylenes, alkynylenes, cycloalkynylenes, arylenes or combinations thereof. Multivalent functional groups optionally include atoms such as —O—, —S—, —Si— and —P— and functional groups such as amide, urea and ester groups.

Preferably, the functional groups according to formula (1) are derived from unsaturated carboxylic acids comprising 2 to 10, preferably 3 to 6 carbon atoms. Carboxylic acids are mono- or polyunsaturated and are monocarboxylic or polycarboxylic acids. Examples of suitable monocarboxylic acids are acrylic acid, methacrylic acid, cinnamic acid, propazic acid and dihydrolevulinic acid. Examples of suitable polycarboxylic acids are citraconic acid, maleic acid, itaconic acid or anhydrides thereof, and Mesaconic acid and fumaric acid. Also monoesters of mono- and polycarboxylic acids and diesters of polycarboxylic acids are for example acrylic esters, maleic acid mononitrile-monoesters, diethyl maleate, cyanoacrylic acid esters as described in WO 98/41561. And alkylidene malonic acid esters. Preference is given to acrylic acid or esters thereof, maleic acid, esters or anhydrides thereof.

When the functional groups according to formula (1) are derived from acrylic acid or esters thereof, suitable examples of compounds comprising two or more olefinically unsaturated groups include trimethylol propane triacrylate.

When the functional groups according to formula (1) are derived from maleic acid, esters or anhydrides, suitable examples of compounds comprising at least two olefinically unsaturated groups are diols which selectively react with polyisocyanates such as 1,5-pentane diol, 1,3 Polyesters of diethyl maleate of propane diol and / or 2-butyl-2-ethyl propane diol; Also epoxy-functional compounds reacted with trimers of isophorone diisocyanates such as Vestanat® T1890E (manufactured by Huel's), such as Cardura®E10 (aliphatic epoxy compound from Shell Chemical Company) and isobutyl monomale Reaction products of the ate; And reaction products of maleic anhydride, dipentaerythritol and butanol.

Optionally, the functional groups according to formula 1 are derived from unsaturated aldehydes.

Finally, compounds comprising at least two olefinically unsaturated groups comprising at least one electron-drawing functional group connected to a carbon atom of an unsaturated bond are unsaturated ketones such as divinyl ketone or dibenzal acetone.

Compounds comprising at least two mercapto-functional groups are prepared by direct esterification of polyols and mercapto-functional organic acids. Examples of mercapto-functional organic acids include 3-mercaptopropionic acid, 2-mercaptopropionic acid, thio-salicylic acid, mercaptosuccinic acid, mercaptoacetic acid or cysteine. Examples of compounds prepared according to the above methods are pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), trimethylol propane tris (3-mercaptopropionate) ), Trimethylol propane tris (2-mercaptopropionate) and trimethylol propane tris (2-mercaptoacetate). Further examples of compounds prepared according to the process include excess polyol cores based on starter polyols, for example trimethylol propane and dimethylol propionic acid. The polyol is fully esterified with 3-mercaptopropionic acid and isononanoic acid. The method is described in European patent application EP-A 0 448 224 and international patent application WO 93/17060. Another example of a compound comprising at least two mercapto-functional groups is a mercaptan functional polyurethane resin. In the first step, isocyanate functional polyurethanes are prepared by making blocks containing functional groups that utilize the stability of the resin in diols, diisocyanates and aqueous dispersions. Such functional groups are, for example, polyethylene oxide derivatives, sodium sulfonate groups and other ion stabilizers. In the second step, isocyanate functional polyurethanes are reacted with di-, tri- or tetra functional thiols such as trimethylol propane trimercapto propionate and pentaerythritol tetramercapto propionate. The equivalent ratio of thiol groups to isocyanate groups in this step is between 2-5: 1. The resin is suitable for waterborne coating compositions.

Optionally, the compound comprising at least two mercapto-functional groups has, for example, a structure according to the following general formula: T [(C ₃ H ₆ O) _n CH ₂ CHOHCH ₂ SH] ₃ (wherein T is Thiols such as trimethylolpropane or glycerol). Examples of such compounds are those manufactured by Henkel under the trade name Henkel Capcure 3/800.

Other syntheses for the preparation of compounds comprising at least two mercapto-functional groups include the following:

Reaction of NaHS with aryl or alkyl halides to inject one mercapto group into the alkyl and aryl compounds, respectively;

Reaction of sulfur Grignard reagent to inject one mercapto group into the structure;

Reaction of polyolefins with polymercaptans in accordance with nucleophilic reactions, such as Michael addition reactions, electrophilic reactions or radical reactions;

Reduction of disulfides; And

Another route as mentioned in Advanced Organic Chemistry, Jerry March, 1992, p. 1298.

It is preferred that the mercapto-functional group and the olefinically unsaturated group are in an equivalent ratio between 1: 2 and 2: 1, preferably about 1: 1.

In an optional embodiment of the invention, a compound comprising at least two olefinically unsaturated groups comprising at least one electron-drawing functional group connected to a carbon atom of an unsaturated bond and a compound comprising at least two mercapto-functional groups is one And the same compound. This embodiment yields a composition capable of self-cross-reacting in the presence of a catalyst comprising at least one NH-group optionally blocked.

The composition of the present invention comprises a catalyst comprising at least one NH-group optionally blocked. Catalysts comprising at least one NH-group are for example primary and secondary amines. Catalysts comprising at least one blocked NH-group are, for example, aldimine, ketamine, enamine and oxazolidine. Also included are catalysts in which the NH-groups are caused by sunlight or UV radiation.

Examples of primary amines are isophorone diamine, butyl amine, n-octyl amine, n-nonyl amine, N, N-diethylamine-propyl-3-amine, 4- (aminomethyl) -1,8-octane diamine , Aniline, methoxy aniline, carboxyl ethyl aniline, phenylene diamine and derivatives thereof. Also included are polyoxyalkylene amines such as polyoxy ethylene / polyoxy propylene mono-, di or triamine. This is a product of Huntsman under the trade name Jeffamine®, such as Jeffamine® T-403.

Suitable secondary amines are, for example, di-octyl amines.

Other suitable catalysts are condensation products of ketimines, ie primary amino groups and ketones or condensation products of aldimines, ie primary amino groups and aldehydes. In the condensation reaction, functional groups of the following general formula are formed:

(Formula)

(Wherein R 5 is an alkyl group, a ring functional group or an aromatic functional group and R 6 is hydrogen in the case of an aldimine or alkyl group, a ring functional group or an aromatic functional group in the case of ketimine. It is preferable that R 5 and / or R 6 are an alkyl group. And / or R 6 is more preferably an alkyl group containing 1-10 carbon atoms.

Examples of aldimines are monofunctional amines such as n-octyl- or n-nonyl amines and isophorone diamines such as acetaldehyde, propionaldehyde, isobutyraldehyde, n-octyl aldehyde, 2-ethylhexyl aldehyde or n-nonyl aldehyde Condensation products of polyfunctional amines. Products are, for example, Vestamine® A139, isophorone bisisobutyraldimine, ex Huels. Also aromatic aldehydes and dialdehydes and heterocyclic aldehydes and dialdehydes and mixtures thereof are used. Examples of aromatic aldehydes include 4-acetamidobenzaldehyde, anthracene-9-carboxaldehyde, 3-benzyloxybenzaldehyde, 4-benzyloxybenzaldehyde, 3-benzyloxy-4-methoxybenzaldehyde, 3,5-bis (tri Fluoromethyl) benzaldehyde, 3-bromo-4-methoxybenzaldehyde, 5-bromo-2-methoxybenzaldehyde, 2-bromobenzaldehyde, 3-bromobenzaldehyde, 4-bromobenzaldehyde, α-bromosin Southern aldehyde, 3-bromo-4-fluorobenzaldehyde, 4-bromo-2-fluorobenzaldehyde, 5-bromo-2-fluorobenzaldehyde, 5-bromo-2-hydroxybenzaldehyde, 2-chloro Benzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde and other halogen substituted aromatic aldehydes, 4-butoxybenzaldehyde, 2,3-dihydroxybenzaldehyde and other isomers, 2,3-dimethoxybenzaldehyde and other isomers, 3,4 Dimethoxy-6-nee Trobenzaldehyde, 4-dimethylaminobenzaldehyde, 2,5-dimethyl-p-anisaldehyde, 2,4-dinitrobenzaldehyde, 4-phenoxybenzaldehyde, 3-phenoxybenzaldehyde, 4-phenylbenzaldehyde, p-tolualdehyde, o-tolualdehyde, and m-tolualdehyde, 2,4,6-trimethylbenzaldehyde and other alkyl substituted benzaldehydes. Examples of aromatic dialdehydes include 1,3-benzenedialdehyde and terephthalaldehyde. Examples of heterocyclic aldehydes include thiophene-2-carboxaldehyde, thiophene-3-carboxaldehyde, 5-acetoxymethyl-2-furaldehyde, 4-bromo-2-thiophenecarboxaldehyde, 3, 5-dimethyl-1-phenylpyrazole-4-carboxaldehyde, 3-phenyl-1h-pyrazole-4-carboxaldehyde, picoline aldehyde, 4-pyridinecarboxaldehyde, 3-pyridinecarboxaldehyde and 4 -Quinolinecarboxaldehyde. Examples of heterocyclic dialdehydes include 2,5-thiophenedicarboxaldehyde.

Suitable ketimines are mono- and polyfunctional amines, for example acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, ethyl amyl ketone, cyclohexanone, acetophenone, hydroxyacetophenone or acetyl biphenyl Condensation product. One example is the reaction product of 3 mol of ethyl amyl ketone and 4- (aminomethyl) -1,8-octane diamine.

An example of a suitable oxazolidine is the reaction product of Incozol® LV (manufactured by Industrial Copolymer Ltd.), ie 1 mole of diallyl carbonate and 2 moles of oxazolidine made from diethanolamine and isobutyraldehyde.

An example of a suitable enamine is 1-pyrrolidino-1-cyclohexene.

The catalyst produced by the NH-group by UV radiation is J. Org . Chem. , 1990, 55, 5919-5922. Examples of catalysts for which the NH-group is made by UV radiation are N-[[1- (3,5-dimethoxyphenyl) -1-methyl-ethoxy] carbonyl] cyclohexylamine, N, N'-bis [ To [1- (3,5-dimethoxyphenyl) -1-methylethoxy] carbonyl] hexane-1,6-diamine, N-[[1- (3,5-dimethoxyphenyl) -1-methyl Methoxy] carbonyl] piperidine, [[1- (3,5-dimethoxyphenyl) -1-methylethoxy] carbonyl] amine, [[(2,6-dinitrobenzyl) oxy] carbonyl] Cyclohexyl amine, 4,4 '-[bis [[2-nitrobenzyl) oxy] carbonyl] trimethylene] dipiperidine, 3,3', 5,5'-tetramethoxybenzoin cyclohexyl carbamate And mixtures thereof.

Optionally blocked NH-acting catalysts may be used alone in a mixture of catalysts of the same nature or in a mixture of catalysts of different properties. In particular, if the composition according to the invention is used as a monomer, it is preferable to use a mixture of aldimine and ketamine as catalyst. The mixing weight ratio can be used 0.1-10: 1, preferably 2-6: 1. This has been known to result in better adhesion to the material.

Since the reaction time depends only on the amount of catalyst in a small range, a high concentration of catalyst can be used without making the reaction difficult to control. It has been found that the enhancement of the sensation and curing time of the base coat or top coat to acidic materials or monomers is lower when higher concentrations of the catalyst according to the invention are used. It is believed that the tertiary amine is further reduced if added to the top coat or base coat composition because it is believed to adhere to the acidic monomers or acidic materials used and neutralize their acidity. The total amount of catalyst is then used to catalyze the reaction. Suitable tertiary amines are N, N-dimethyl-ethanol-amines.

It is preferred that the catalyst is used in amounts of 0.01-10 equivalent% nitrogen groups based on total unsaturation and thiol groups. More preferred is an amount of 0.1-6 equivalent%.

The composition according to the invention is a water soluble composition, a solvent composition or a solventless composition. Since the composition consists of low viscosity oligomers, it is particularly suitable for use as a high-solid coating or solvent-free coating. The theoretical volatile organic content (VOC) of the composition is preferably 450 g / l or less, more preferably 350 g / l or less, most preferably 250 g / l or less.

In order to further reduce the volatile organic content, reaction diluents such as diethyl maleate, methoxypropyl citraconimide, diethylbenzylidene malonate, α, β-unsaturated aldehydes such as cinnamic aldehyde or citral, and Monothiol functional compounds such as dodecyl mercaptan and mercapto functional silanes such as γ-mercapto-propyl-trimethoxysilane are used. Mercapto-functional groups and olefinically unsaturated groups of the reaction diluent are also contemplated in accordance with the above-mentioned equivalent ratios.

The composition is particularly advantageous for coating compositions or adhesives. Preferably, a two-pack composition is used. It is preferred that the primary content of the two-pack coating or adhesive comprises not only compounds comprising at least two olefinically unsaturated groups, but also compounds comprising at least two mercapto-functional groups, while the secondary content of the composition is small. Catalyst solution. However, if so desired, the secondary content includes some or all amounts of a compound comprising a catalyst followed by an olefinically unsaturated group or a compound comprising a mercapto-functional group.

Formulations include pigments, effect pigments, such as some aluminum, UV absorbers, adhesion promoters, such as epoxy silanes, HALS-type stabilizers, fluid additives or other additives.

The composition according to the invention can be applied by conventional methods including spraying, brushing, roller coating or wetting. However, the compositions of the present invention are particularly suitable for application by an external mixing device, wherein at least one NH group injected into the spray of the sprayed composition, in which one of the liquid compositions comprising Sprayed with a small amount of the liquid catalyst composition comprising at least one catalyst comprising.

Compounds comprising at least two olefinically unsaturated groups comprising at least one electron-drawing functional group connected to a carbon atom of the unsaturated group and

Compounds comprising at least two mercapto-functional groups.

Such apparatus is described, for example, in WO 98/41316. Due to the very effective use of the catalyst, the composition according to the invention has a very short curing time which makes the process particularly suitable for the composition.

The compositions according to the invention can be used for various kinds of industrial applications, in particular wood, plastic and metal materials such as aluminum, steel or plated iron. The composition can be used, for example, as an adhesive or a coating such as an abrasive, primer, filler, base coat, top coat or clear coat. The compositions are particularly advantageous for use as automotive repair coatings because they can be easily sprayed and applied at room temperature. In auto repair in general, it is necessary that some layers be applied to the primer, base coat and clear coat, for example. Because of the short drying time, the next layer can be applied within a short time from the primary layer application.

The invention is further illustrated by the following examples.

In the following examples, compounds of the following list are useful for indicating.

compound Explanation manufacturer Autobase ^® Solvent Base Coat Akzo Nobel Car Refinishes Autocryl ^® 3110 Filling Akzo Nobel Car Refinishes Autocryl ^® LV Solvent top coat Akzo Nobel Car Refinishes Autowave ^® Waterborne base coat Akzo Nobel Car Refinishes Byk ^® 306 Substance Wet Additive BYK-Chemie Byk ^® 333 Silicone fluid additives BYK-Chemie Cardura ^® E10 Aliphatic epoxy compounds Shell chemical company Disperbyk ^® 110 Dispersant BYK-Chemie Incozol ^® LV Oxazolidine Industrial Copolymers Ltd Jeffamine ^® T 403 Primary Triamino-functional Polyalkylene Oxides Huntsman corporation Sparkle Silver ^® E 5000 AR Aluminum paste without leafing Silberline ltd Tinuvin ^® 1130 UV absorbers Ciba Tinuvin ^® 123 Sterically hindered amine light stabilizer Ciba Tinuvin ^® 292 Sterically hindered amine light stabilizer Ciba Vestamin ^® A139 Isophorone bisisobutyraldimine Huels Vestanat ^® T1890E Trimer of isophorone diisocyanate Huels Washprimer ^® CR primer Akzo Nobel Car Refinishes

In the examples, the following abbreviations are used as the compounds as indicated.

DBU diazabicyclo undecene

DMEA N, N-dimethyl-ethanol-amine

IPDA isophorone diamine

PTMP pentaerythritol tetrakis (3-mercaptopropionate)

Of TAN-EAK 3 mol of ethyl amyl ketone and 4- (aminomethyl) -1,8-octane diamine

Reaction product

TMP (2MA) 3 trimethylol propane tris (2-mercaptoacetate)

TMP (3MPA) 3 trimethylol propane tris (3-mercaptopropionate)

TMPTA Trimethylol Propane Triacrylate

In an embodiment, mercapto-functional groups and olefinically unsaturated groups are present in the coating composition in an equivalent ratio of 1: 1.

Curing time was measured using a BK dry recorder. Cure time is the time between application of the sample and the phase when the pen of the BK Dry Recorder no longer damages the material under the coating (Phase III).

The coating is free to handle when the mark on the membrane disappears after 1 or 2 minutes by pressing with a thumb.

Viscosity is measured with a Cone and Plate viscometer, type CAP 2000.

The cross-cutting was made with an Olfa® cutter at 45 °, the standard type adhesive tape was affixed to the paint and gently pulled off again and then tested for adhesion using a so-called pull-of test. Values 1-10 represent the scale for the evaluation of the adhesion range from very poor adhesion (1) to good adhesion (10).

Gitterschnitt adhesion was measured according to ISO 2409. Adhesion is visually determined on a scale from 0 (= not attached) to 5 (= total attachment). The concentration test used with the jitterschnit adhesion test had the following conditions: 10 days at 42 ° C., 100% relative humidity.

Stone chip resistance was measured according to Ford standard test Ford 57-4. Values 0-7 represent the scale for the range evaluation of very bad (7) to good (0) stone chip resistance.

Accelerated weathering tests were conducted according to international standard ISO 2810.

Bubble presence in the cured layer was tested according to ASTM-D714. The results are defined as additional codes for bubble densities ranging from 1 (large bubbles) to 10 (no bubbles), F for "slight", M for "medium" and D for "dense".

Example 1 Preparation of Maleate-Action Polyester

The 2-L4-neck flask was equipped with a thermocouple combined with a variable stirrer, regulator, distillation column, condenser, nitrogen sparge and heating mantle. The flask was charged with 1240 grams of diethyl maleate, 235 grams of 1,5-pentane diol, 360 grams of 2-butyl-2-ethyl propane diol, 3.7 grams of dibutyl tin oxide catalyst and 5 wt.% Xylene. . Nitrogen sparging and agitator were turned on. The heating mantle was set up to heat the reactor charge to 150 ° C. with the top of the column limited to 79 ° C. Ethanol was collected and when the distillation rate was reduced, another amount of 5 wt.% Xylene was added for about 60 minutes and the reaction was carried out under reduced pressure. At the end of the amount of xylene, it was distilled off with ethanol residue. The reaction conversion measured in the amount of ethanol is greater than 98%. The solids content of the final product was 99.6%. The viscosity at 23 ° C. was 1 Pa · s. The maleate number was 278 mg KOH / g solid.

Example 2 Preparation of Maleate-functional Oligo-Urethanes

The 2-L4-neck flask was equipped with a thermocouple combined with a variable speed stirrer, regulator, reflux condenser, nitrogen sparge and heating mantle. 375 grams of Cardura® E10 was placed in the flask. The nitrogen sparging and stirrer were turned on and the batch charge was heated to 100 ° C. Next, 260 grams of isobutyl monomaleate and 0.64 grams of chromium (III) 2-ethyl hexanoate were added while maintaining the batch temperature at 120 ° C. (exothermic reaction). The reaction was run at 120 ° C. and cooled to 80 ° C. until COOH-conversion was at least 98%. 0.5 grams of dibutyl tin dilaurate catalyst was then added and 525 grams Vestanat® T1890 E was added while maintaining the batch temperature below 90 ° C. The reaction was terminated when the NCO conversion reached at least 98%. The product is cooled and diluted with n-butyl acetate to get 70 wt.% Solids. The measured solids content of the resulting product was 72.4%. The viscosity at 23 ° C. was 1.9 Pa · s. Maleate number was 84 mgKOH / g solid.

Example 3 Preparation of Mercapto-Action Polyester

The 2-L5-neck flask was equipped with a thermocouple combined with a variable speed stirrer, regulator, Vigreux column, condenser, nitrogen sparge and heating mantle. Into the flask was charged 48 grams of trimethylol propane, 763 grams of dimethylol propionic acid and 20.5 grams of para-toluene sulfonic acid. Nitrogen sprayed and heated mantle turned on. The stirrer was turned on when the batch charge melted. The first step of esterification at 140 ° C. was carried out until the acid value reached 10 mgKOH / g solids or less. Next, 108 grams of isononanoic acid were added and washed with about 5 wt.% Xylene. The batch solution was cooled to 120 ° C. for the same time. Next, 582 grams of 3-mercaptopropionic acid were added for about 60 minutes and washed with 5 wt.% Xylene. The batch temperature was increased to 140 ° C. while 3-mercaptopropionic acid was added. The second step of esterification was carried out at 140 ° C. with addition of 10 grams of para-toluene sulfonic acid until the acid value reached 15 mgKOH / g solids or less, and refluxed under xylene. 6 grams of lithium carbonate was then added, cooled and diluted with n-butyl acetate to a solid content of 81 wt.%. The precipitate was completed by filtration at about 70 ° C. using a pressure filter as the filter aid to obtain a clear resin. The total OH- and SH-values of the resulting product were 254 mgKOH / g solid. Solids content was 81.8%. The viscosity at 23 ° C. was 1.3 Pa · s.

Example 4-11. Comparative Examples A and B

In Examples 4-11 and Comparative Examples A and B below, coating compositions were prepared comprising 40 g PTMP and 36 g TMPTA. Other catalysts were used as shown in Table 1 below. In Examples 4-11, the catalyst according to the invention was used. The catalysts in the art were used in Comparative Examples A and B. In both Examples 4-11 and Comparative Examples A and B, 0.5 equivalent percent of catalyst was used. The composition was prepared and actually applied to the glass plate using a 200-micron drag bar. The sample was cured at 21 ° C.

Example catalyst Curing time 4 IPDA <1 min 5 1-N, N-diethylaminopropyl-3-amine 1 minute 6 Dioctyl amine 2 minutes 7 IPDA bisnonyl aldimine 12 minutes 8 TAN-EAK 5 minutes 9 1-pyrrolidino 1-cyclohexene 8 minutes 10 Vestamin ^® A139 12 minutes 11 Incozol ^® LV 105 minutes A Triethylamine > 24 hours B Sodium ethanolate > 24 hours

In Examples 4-11 and Comparative Examples A and B, the theoretical VOC was 165 g / l.

Comparative Examples A and B demonstrate that tertiary amine and sodium ethanolate catalysts are not highly effective at room temperature when compared to the catalysts according to the invention at the same concentration. Examples 4-11 show the relative effects of other catalysts according to the invention. The cure time is much shorter than the cure time in Comparative Examples A and B.

Example 12-14

But using different amounts of catalyst, i.e. Vestamine ^® A139 was repeated for Example 10. In Example 10 the equivalent molar amount of catalyst corresponds to 2 wt.%. Corresponding to the test results as shown in Table 2 indicates the sense of the system in the amount of catalyst used.

Example catalyst amount Curing time 12 Vestamine ^® A139 0.5wt.% 22 minutes 13 Vestamine ^® A139 1wt.% 15 minutes 10 Vestamine ^® A139 2wt.% 12 minutes 14 Vestamine ^® A139 3wt.% 10 minutes

In this example, the theoretical VOC was 165 g / l.

Comparative Examples C and D

Comparative Example A was repeated except using a different catalyst, ie DBU in different amounts. As shown in Table 3, the test results show that the use of DBU as a catalyst causes excessively fast reactions of relatively low catalyst concentrations or no cross reactions at somewhat lower concentrations. The same thing happens with other strongly basic catalysts.

Comparative Example catalyst amount Curing time C DBU 0.2wt.% << 1 minute D DBU 0.1wt.% > 24 hours

In this comparative example, the theoretical VOC was 165 g / l.

Example 15

The coating composition included 40g PTMP of Example 1 and 64.8g of maleate-acting polyester. The catalyst used was 2 wt.% Vestamine ^® A139 (2.3 equiv.). Theoretical VOC was 400 g / l. Application was made according to example 4. Curing time was 22 minutes at 21 degreeC.

Example 16 and Comparative Example E

In Example 16 and the corresponding comparative example E, 31.2 g of PTMP was used in combination with 50 g of maleate-acting polyester as prepared in Example 1. In Example 16, 1.5 wt.% Vestamine ^® A139 was used as catalyst (1.7 equiv.). In Comparative Example E, DMEA was used as the amount equivalent molfh catalyst to the amount of catalyst in Example 16. Theoretical VOC was 250 g / l for both Example 16 and Comparative Example E. The composition was added to the material in the same manner as in Example 4. The curing time for Example 16 is 20 minutes, whereas the curing time for Comparative Example E is at least 24 hours at 21 ° C.

Examples 17, 18, 19 and Comparative Example F

The following primer / filler formulations were prepared:

15.21 grams of mercapto-acting polyester of Example 3

Disperbyk ^® 110 0.40 grams

6.26 grams of butyl acetate

14.20 grams of calcium carbonate

5,70 grams of magnesium silicate

14.00 grams of titanium dioxide

6.30 grams of zinc orthophosphate

0.04 grams of low color furnace black

13.80 grams of maleate-acting polyester of Example 1

To give the composition the required viscosity for spraying, another 10.00 grams of butyl acetate was added.

The primer / filler formulation was added to the steel substrate by spraying with an external mixing device using another catalyst and the thickness of the coating layer was 80μ after curing at 21 ° C. In Example 17, 2.5 equivalent% TAN-EAK was used. After 5 minutes the filling material was rubbed with sandpaper. In Example 18, 2.5 equivalent% IPDA was used. The filling material was rubbed with sandpaper after 30 minutes.

In Example 17 as well as in Example 18, the theoretical VOC was 290 g / l.

The composition was added to the steel substrate by spraying with an external mixing device as prepared in Example 18. In Comparative Example F, it was added a Autocryl ^® 3110 filler in a steel base. In fact, all primed substrates were treated with a top coat, Autocryl ^® LV. Curing took place at a temperature of 23 ° C. for several days. The sample was then immersed in water for several days after assessing the cross-cut adhesion of the primer to the steel substrate. The results are shown in Table 4.

To the composition prepared in Example 18 was added an adhesion promoter, 4% by weight solid binder of the epoxy silane (Example 19). The same test was carried out as mentioned above. The results are also disclosed in Table 4.

Primer / Steel Adhesive Immersion (Days): 0 One 7 14 recovery bubble Comparative Example F 8 8 8 8 9 9F Example 18 9 One - - 9 9F Example 19 9 10 9 9 9 9F

For the following tests, the samples used the compositions of Example 18 and Comparative Example F. The primer samples were added to substrates pre-treated with Washprimer ^® CR. Indeed, a top coat, Autocryl ^® LV, was added to the primer. Curing occurred at 21 ° C. The results are shown in Table 5 below.

Stone chip resistors Jitter knit Accelerated weathering Sample Before immersion After immersion Before concentration test After concentration test Adhesion Loss in mm Example 18 3 6 0-1 One 1.5 Comparative Example F 3 6 0-1 One One

Example 20

In the above examples, base coats were prepared according to the present invention.

PTMP 60.00 g

97.41 grams of maleate-acting polyester of Example 1

Sparkle Silver ^® E 5000 AR 48.43 g

Butyl Acetate 69.58 g

Theoretical VOC was 165 g / l. It was added by spraying to pre-coated steel base material for the base coat formulation with Autocryl ^® 3110 filler. The base coat was added to the external mixing apparatus described above using 2.5 equivalent% TAN-EAK. The resulting film was oversprayed after 7 minutes curing at 21 ° C.

Example 21

A clear coat was prepared comprising the following compounds:

PTMP 120.00 g

96.90 g TMPTA

Butyl acetate 36.00 g

Byk ^® 306 0.85 grams

Tinuvin ^® 292 1.08 g

Tinuvin ^® 1130 2.17 grams

Theoretical VOC was 435 g / l. The formulation was sprayed with an external mixing apparatus with TAN-EAK of 5 equivalent% catalyst solution. The layer thickness was 50μ after curing. When sprayed onto various commercial base coats, such as Autobase ^® and Autowave ^® , they are free to handle after 10 minutes of curing at room temperature.

Example 22

Another clear coat was made with the following formulation:

PTMP 13.24 grams

100.00 grams of maleate-functional oligo-urethane of Example 2

Butyl Acetate 44.94 Grams

Tinuvin ^® 123 0.48 grams

Tinuvin ^® 1130 0.48 g

Byk ^® 333 0.27 grams

The formulation was crosslinked with Vestamine ^® A139 in 5 equivalent% catalyst solution and added, cured and tested as in Example 21. The clear coat formulation is free to handle after 20 minutes of curing at room temperature.

Example 23

Dyeing agents were prepared including maleate-acting pastes, mercapto-acting pastes and catalysts.

Maleate-acting pastes comprising:

5.7 grams of titanium dioxide

12.1 grams of barium sulphate

82.2 grams of magnesium silicate

100.0 grams of maleate-acting polyester of Example 1

Mercapto-acting face including:

2.8 grams of titanium dioxide

6.1 grams of barium sulfate

41.1 grams of magnesium silicate

PTMP 23.5 grams

When the two pastes and the catalyst were mixed, an abrasive was added to the steel substrate and cured at 21 DEG C, followed by a processing time of 3.5 minutes, solid after 4.5 minutes, and rubbed with sandpaper after 10 minutes.

Example 24

The catalyst was prepared as Vestamine ^® A139 (2.75 equivalent weight%), and the composition of Example 23, except that the substituted. After being applied to the steel substrate and cured at 21 DEG C, a processing time of 5.5 minutes was obtained, and after 41 minutes, a solid was obtained which was abrasive after 1 hour or more.

Examples 25 and 26

In Examples 25 and 26 two water based clear coats according to the invention were made.

Acryloyl-functional polyurethane emulsion (43% sc in water, solid weight 454 C = C equivalent) was mixed with TMP (3MPA) 3 (60% sc in methoxy propyl acetate). In Example 25, the composition was cured with IPDA (5 equiv), while in Example 26, the composition was cured with Jeffamine ^® T 403 (2.7 equiv).

The clear coat was applied to the glass substrate using a 100-micron drag bar and cured at 21 ° C.

Example 25 Example 26 Acryloyl-functional Polyurethane Emulsion 31.8 grams 31.8 grams TMP (3MPA) 3 6.7 grams 6.7 grams IPDA 0.28 grams - Jeffamine ^® T 403 - 0.24 grams Curing time 24 minutes 32 minutes

Example 27-35

In Examples 27-35 below, the coating composition was prepared comprising the maleate-functional polyester and mercapto-functional and olefinically unsaturated groups of Example 1 in combination with other mercapto functional compounds in a ratio of 1: 1 equivalents. The other catalyst was used in an amount of 0.75 equiv. The composition was added to the glass plate using a 200-micron drag bar. The sample was cured at a temperature of 21 ° C. Table 7 discloses cure times.

Example Incozol LV 27 PTMP 90 28 TMP (3MPA) 3 94.8 29 TMP (2MA) 3 21.3 Vestamine A139 30 PTMP 20.4 31 TMP (3MPA) 3 33.8 32 TMP (2MA) 3 29.7 TAN / EAK 33 PTMP 5.2 34 TMP (3MPA) 3 5.6 35 TMP (2MA) 3 <1

Claims (10)

A composition comprising the following. Compounds comprising at least two olefinically unsaturated groups comprising at least one electron-drawing functional group connected to a carbon atom of an unsaturated bond; Compounds comprising at least two mercapto-functional groups; And A catalyst comprising at least one NH-group optionally blocked. The method of claim 1, Wherein said catalyst is selected from primary or secondary amines, aldimines, ketimines, enamines, oxazolidines or mixtures thereof. The method according to claim 1 or 2, Wherein said catalyst is used in an amount of 0.01-10 equivalent% nitrogen groups based on the total of unsaturated and thiol groups. The method according to any one of claims 1 to 3, Composition wherein the oleic pin unsaturated group of the compound comprising two or more olefinic unsaturated group has a structure according to the formula (1). (Formula 1) (In Formula 1, at least one of R 1, R 2, R 3 and R 4 includes an electron-drawing functional group connected to a carbon atom of an unsaturated bond and at least one of R 1, R 2, R 3 and R 4 is connected to at least a divalent polyvalent functional group. do.) The method of claim 4, wherein The electron-drawing functional groups are carbonyl, carboxyl, ester, thiocarbonyl, thiocarboxyl, thioester, sulfoxide, sulfonyl, sulfo, phosphate, phosphite, phosphonite, phosphinite, nitro, nitrile and Composition selected from amides. The method of claim 5, At least one functional group according to formula 1 is characterized in that derived from an unsaturated carboxylic acid containing 2 to 10 carbon atoms. The method according to any one of claims 1 to 6, Wherein said mercapto-functional group and olefinically unsaturated group are present in an equivalent ratio between 1: 2 and 2: 1. Wherein a small amount of the liquid catalyst composition comprising at least one catalyst comprising at least one NH-group blocked with a liquid composition is sprayed through a spray nozzle and optionally blocked, is injected into the spray of the sprayed composition Method for applying the composition according to any one of claims 1 to 7. Compounds comprising at least two olefinically unsaturated groups comprising at least one electron-drawing functional group connected to a carbon atom of an unsaturated bond; And Compounds comprising at least two mercapto-functional groups. Use of the composition according to claim 1 as a coating composition. Use of the composition according to any one of claims 1 to 7 as an adhesive.